JPS60163978A - Rust-resisting paint - Google Patents

Abstract

PURPOSE:To obtain a rust-resisting paint which has excellent environmental barrier properties, flexibility, impact resistance, multiple coating adhesion and adhesion to substrates, can be thick-coated and is economical, by mixing a butyl rubber paint component with a cement component. CONSTITUTION:A rust-resisting paint consists of a butyl rubber paint component (A) consisting of a vehicle, a filler, additives and an org. solvent and a cement component (B). The vehicle is a coating film-forming component in the paint and examples thereof are butyl rubber, a phenolic resin and tar pitch. Examples of the additives are plasticizer, anti-foaming agent, leveling agent, lubricant, surfactant, coupling agent, etc. which may be optionally used. Insecticide, antifouling agent, preservative, mildewproofing agent, etc. (e.g. high-molecular organotin compd., org. and/or inorg. copper compd., organosulfur compd., etc.) may be added thereto to prevent the coating film from being deteriorated by harmful living organisms.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a rust preventive paint, and more particularly to a rust preventive paint comprising (4) a butyl rubber paint component and (B) a cement component.

The feature of the present invention is that it fully utilizes the strength of the bond between butyl rubber and cement, as well as the excellent environmental barrier properties, flexibility, impact resistance, and adhesion of butyl rubber. That is, in the present invention, rubber is used as a binder for cement, and the cement is cured by steam curing the coated object of the present invention's paint, or by moisture resistance under the conditions of use. This provides a stronger coating on the back side.

More specifically, in general, it is possible to easily make a cement-containing paint by dissolving a polymer compound in a suitable solvent and dispersing cement therein, but general polymers have poor bonding strength with cement. Cement is weak and can only be used as a filler, so by increasing the blending ratio of cement, it becomes even more water resistant, chemical resistant,
Weather resistance is lost, resulting in a paint with poor durability. death! ...Kashita et al., butyl rubber was produced by special public corporation in 1974-608.
As is known as No. 8 No. 1, it is a polymer that has very strong bonding strength even to green mortar and exhibits excellent adhesion to green mortar among many other polymers. Therefore, when butyl rubber is used as a binder, when the cement absorbs water and hardens, the bonding force at the interface between butyl rubber and cement becomes even stronger, and the peeling phenomenon seen with other types of polymers is not observed.

In addition, as is well known, butyl rubber has excellent environmental barrier properties such as watertightness and airtightness, and is also a material with excellent flexibility, impact resistance, recoat adhesion, and adhesion to the substrate. It is.

On the other hand, it is well known that cement is a material that undergoes a hardening reaction with moisture and becomes extremely hard, and has been used for various purposes since ancient times, and is still used in a huge amount today. However, conventional butyl rubber-based paints, rather than rubber-based paints, have poor paintability, especially when forming a film at room temperature, as a crosslinking method has not been put into practical use to obtain sufficient film strength. However, they tend to have disadvantages such as poor viscosity stability of the paint and easy adhesiveness of the paint film, and only a few products such as Hypalon chloride rubber and cyclized rubber have been put into practical use.

On the other hand, cement-based paints such as polymer cement, latex cement, emulsion cement, and cement (IJ resin) are currently in practical use and have many advantages, but all paint films suffer from drying shrinkage and hardening shrinkage. It has problems in terms of construction and curing location, such as cracks due to various factors, poor impact resistance, poor adhesion to the base, poor adhesion to the base, and long curing period.

Therefore, the inventors of the present invention have been working for a long time to improve environmental barrier properties, flexibility,
Impact resistance, recoat adhesion, adhesion to the base, toughness,
As a result of extensive research in order to obtain a rust-proofing paint that has excellent abrasion resistance, can be applied thickly, and is highly economical, the object of the present invention is a rust-proofing paint consisting of a butyl rubber component and a cement component. We have completed the present invention by confirming that the above conditions are met.

Next, the constituent components of the present invention will be explained.

Component (A) described in the present invention is a butyl rubber coating component, and as explained below in sequence, the component (A) is a color vehicle, filler,
This is a butyl rubber coating I consisting of additives and an organic solvent.

That is, the color vehicle refers to a coating film-forming component of a paint, and those that can be used in the present invention include butyl rubber, recycled butyl rubber, polyisobutylene, chirhenic resins, terpene-phenolic resins, phenolic resins, and carbonized aromatic resins. hydrogen resin,
Examples include alicyclic hydrocarbon resins, aliphatic hydrocarbon resins, xylene resins, coumaron-indene resins, rosin and rosin-modified resins, straight asphalt, butene asphalt, and tar pitch. 1 (1 but
In the present invention, the butyl rubber component is 2 in the composition of the color vehicle.
It is preferable that the content is 0 to 80% by weight. The butyl rubber component described in the present invention refers to a rubber component comprising one or more of butyl rubber, recycled butyl rubber, and polyisobutylene. The characteristics of the butyl rubber component are gas barrier properties against corrosive substances such as oxygen, chlorine, sulfur dioxide, and water vapor, water resistance, salt water resistance, chemical resistance against acids and alkalis, weather resistance, aging resistance, and bending resistance. As is well known, it has excellent properties such as high electrical insulation resistance, and is a component that has particularly excellent insulation ability.

When butyl rubber was less than 20% by weight in the composition of the color vehicle constituting component (A), the environmental barrier properties and flexibility tended to be poor. On the other hand, if the content was 80% by weight or more, the toughness, viscosity stability, and coating workability tended to be poor.

Another important thing about butyl rubber paint components is the need to adjust their plasticity.

In other words, one of the reasons why rubber-based paints have not been put to practical use is the poor solubility of rubber and the viscosity stability after dissolution. Therefore, we adjusted the plasticity of the polymer.If the plasticity is high, there will be problems with solubility and/or paint viscosity, and if the plasticity is low, it will have a negative impact on the coating strength and the adhesion of the coating surface. gave me peace of mind.

In the present invention, the optimum Mooney viscosity is ML1+4(10
0°C) within the range of 80 to 50, and by improving the blending ratio of fillers and adhesion-imparting resins, their types, and their mixing and dissolving methods, problems with solubility and viscosity stability can be solved. I ended up resolving it.

In addition to the above-mentioned butyl rubber component, examples of the color vehicle constituting the butyl rubber coating component (A)I& of the present invention include a tackifying resin component and a bituminous material.

Adhesion-imparting resin components include terpene resins, terpene-phenol resins, phenol resins, and coumarons.
Indene resins, xylene resins, rosin and rosin-modified resins, aromatic hydrocarbon resins, alicyclic hydrocarbon resins, aliphatic hydrocarbon resins, etc. are used singly or in combination of two or more.

The effects of using the adhesion-imparting resin are improvements in adhesion to the base and the base for recoating, coating film strength, solubility, and viscosity stability.

As the bituminous component, straight asphalt, blown asphalt, tar pitch, etc. may be used alone or in combination of one or more.

The effects of using bituminous materials include improved corrosion protection, improved fillability of fillers, improved solubility, improved viscosity stability, and cost reduction.

The fillers described in the present invention include clay, Yu!・□Luc, mica, white carbon, carbon, asbestos, barium sulfate, calcium carbonate, silica sand, shirasu balloon, glass peas, titanium oxide, iron oxide, zinc oxide,
White lead, red lead, basic lead sulfate, zinc chromate, zinc phosphate, molybdenum mg lead =.

Ferrite, metal zinc powder, etc. are used alone or in combination of two or more. The effects of using fillers include adjusting workability and viscosity to prevent sagging during thick coating, adjusting the mixing ratio in product form, adjusting solid content, improving solubility, improving anti-corrosion effects, and preventing slipping at the end of coating. etc.Il+.

The additives described in the present invention include plasticizers, antifoaming agents, leveling agents, lubricants, surfactants, coupling agents, etc., and can be selected and used as necessary.

In addition, insect repellent, antifouling, antiseptic, and preservative agents such as high-molecular organic tin compounds, copper-based organic and/or inorganic compounds, and organic sulfur compounds are added to prevent deterioration of paint films caused by various harmful organisms and are useful in sewage-related applications. It is also possible to further increase the durability of parts that are susceptible to biological deterioration, such as facilities, underwater structures, inner walls of headrace channels, and submerged parts of ship shells. ``The organic solvents described in the present invention refer to organic solvents such as aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, ethers, esters, and ketones. One or more of these can be used in combination.

In the present invention, as in general coating formats, the selection of solvent affects coating film performance, workability, and coating film appearance, so the combination of main solvent and co-solvent must be carefully selected. In addition, the present invention is dried at room temperature, and if a high boiling point solvent with a boiling point of 150°C or higher is mainly used for thick coating, the solvent will not come out easily and will have an adverse effect on adhesive properties, chemical resistance, etc. Avoid using low-boiling point solvents with a boiling point of 100°C or less and/or boiling points of 1.
It is preferable to mainly use a medium boiling point solvent of 00°C to 150°C.

In the present invention, 03) Cement) It content refers to ordinary Portland cement, early-early-strength Portland cement, ultra-early-strength Portland cement, medium, high-early-strength Portland cement, sulfate-resistant Portland cement, white cement, super quick-hardening cement, alumina cement, A general term for hydraulic cements such as silica cement, blast furnace cement, and fly ash cement, and/or cements prepared by pre-mixing hydraulic cement and admixtures, and used singly or in combination of two or more. However, among these, cements containing expanded polystyrene and powdered polystyrene polymer compound dissolve in the solvent in the ingredients mentioned above, causing an increase in viscosity, and as mentioned above, cement The low bonding strength after water absorption and curing adversely affects coating workability and durability, making it undesirable.

As stated repeatedly in the present invention, the cement component provides toughness and strengthens the bonding force with the butyl rubber component, so any of the above cement component examples can be used, but the product Considering the case of a two-component type, ordinary Portland cement is preferred because it is easily available and inexpensive throughout the country.

When producing the anti-corrosive paint of the present invention, the butyl rubber component and some or all of the fillers and additives are added and kneaded using a mill, kneader, Banbury mixer, or general-purpose rubber kneader. After dissolving and dissolving in an organic solvent to make a rubber solution, add the remaining fillers and additives if there are any, stir and mix, pass through a paint roll mill to create a butyl rubber paint, and when used, cement It is a two-component anti-corrosion paint that is mixed with Furthermore, if necessary, a one-component rust-preventing paint can be obtained by mixing a fraction of cement with the butyl rubber paint.

However, the above manufacturing method is only an example, and the present invention is not limited to this.

The method of using the anti-corrosion paint of the present invention is to use the one-component type as is, and to use the two-component type, measure the mixture to a predetermined ratio and mix thoroughly, then use airless spray, air spray, brush coating, roller coating, etc. Dry at room temperature by troweling, etc. In addition, in order to achieve a predetermined thickness, repaint the coat after a predetermined drying time and dry at room temperature. Next, regarding the curing conditions, there are cases where the cement is left to dry at room temperature and allowed to harden naturally with moisture such as rainwater during use, and cases where the cement is hardened with steam. Although there is a difference in the time required for the initial surface hardness to develop depending on which method is used, there is no difference in physical properties such as anti-corrosion durability among the methods.

The product form of the anti-rust paint of the present invention is described below: (2) A two-component anti-rust paint in which the butyl rubber paint component and the cement component are separated.

(2) A one-component antirust paint containing both a butyl rubber paint component and a cement component.

The above-mentioned two product forms can be taken, and storage stability and physical properties of the cured coating film are the same in either form.

Next, the effects of the antirust paint of the present invention will be explained.

As mentioned above, the anti-rust paint of the present invention is a combination of cement and butyl rubber, which is a polymer that has a bonding force with raw mortar, and is a new type of paint that is not in the category of conventional paints. .

In other words, it completely shuts out low hardness, which is the biggest drawback of rubber paints, and cracking, which is the biggest drawback of cement paints, and has environmental barrier properties derived from the butyl rubber component.
It has the advantages of impact resistance, bending resistance, adhesion between coatings, and adhesion to the base.
It has the advantages of toughness and economy. In addition, the high solid content paint allows thick coating, and the process is shortened by reducing the number of coats.
Butyl rubber has many advantages in terms of labor saving, energy saving, cost reduction, improved corrosion resistance, less volatile solvents, improved occupational safety and health, and lower paint prices. When recycled butyl rubber, which is obtained by recycling car tire tubes, is used as a component, it also has the advantage of effective use of resources.

In this way, the anti-rust paint of the present invention does not combine the advantages of butyl rubber and cement, which have not been seen in the conventional paint field, but focuses on the strong bonding force of butyl rubber and cement, and combines their comprehensive strength. It is a paint in a new field that was invented, and it is useful for the development of various industries by taking advantage of its environmental barrier properties, increased hardness, and economic efficiency, and greatly extending the life cycle of the coated object. .

Next, see examples of the present invention and comparative examples for more details!゛′(
12) However, the present invention is not limited in any way by the following examples.

■Preparation method of test sample 1 Preparation of anti-rust paint of the present invention (A) Preparation of butyl rubber paint component Add the butyl rubber component, filler, adhesion imparting resin and bituminous material, and use a pressure kneader at 50 to 70°C. Mix the compound to make it sufficiently uniform, swell the compound sufficiently with an amount of organic solvent to make the solid content 80%, dissolve it with stirring, and when it becomes sufficiently uniform, mix it with an ink rule. After the treatment, the remaining organic solvent was added to achieve a sufficiently uniform state.

(4) Mixing Butyl Rubber Paint Component and (B) Cement Component A predetermined amount of cement was mixed with the butyl rubber paint component I8 obtained by the above method to obtain a sufficiently uniform state to obtain a rust preventive paint.

a Preparation of sample Apply a predetermined amount of the anti-rust paint prepared using the above method to the predetermined object to be coated using a film applicator! (After drying at room temperature for more than one day, steam curing was performed at 80°C for one day.

■Test method - Measuring method for environmental barrier properties 1-1 Water resistance: According to JIS-54.00 (7°2), the temperature for row 1 cattle is 50℃±2℃, humidity 98±2, and the holding time is 96. It was time.

1-1 Salt water resistance: According to JIS-5400 (items 7 and 6). i... 1-& weather resistance: JIS-5400 (7.

17), the conditions are The irradiation was carried out for 1000 hours.

2 Adhesion measurement method 2-1 Substrate adhesion; JIS-54001 (6115
Section).

2-2-Recoating adhesion: JIS-5400 (6,
Recoating was performed according to Section 10), and adhesion was examined according to JIS-5400 (sections 6 and 15).

& How to measure flexibility 8-1 Impact resistance: JIS-54100 (6.

18.8). -・ 4L@Toughness measurement method 4-L pencil hardness: tTIS-5400 (6.

14).

& Measuring method of chemical resistance 5-L Acid resistance: tTIS-5400 (7*l...5
Section).

fi-L alkali resistance: JIS-5400 (7,4
Section).

a Method for measuring painting workability 6-1 Painting workability - Keep the paint vertical when spraying l) Approximately 1IIl on the iron plate surface! A rust preventive agent was sprayed to a thickness of No. 1 under the following conditions, and the finished state of the coating film after curing was checked.

Spraying is a condition Painter: Airless gun AL18-122
Mold (manufactured by Iwata Paint Industry Co., Ltd.) Pressure magnification: 1:20 Air pressure: 5 kg/cm" Nozzle diameter: 0.4 m How to measure I viscosity stability? - L (sub) butyl rubber paint component and (B) Add a predetermined amount of cement ingredients, mix thoroughly, create a sufficiently uniform rust-preventive paint, and apply I/P at room temperature.
After standing for a period of time, the viscosity before storage was measured using a B-type viscometer.

Next, after storing at room temperature for 8 months, The viscosity was measured in the same manner as Kuramae. Savings The rate of viscosity change before and after storage was calculated using the formula below.

& Relationship of moisture to hardness after drying and curing 1-1 Obtained by producing the anti-corrosive paint of the present invention 2... It was coated on the paper and dried for 7 days in a constant temperature dryer at 50°C.

Next, it was left to cool in a desiccator for 4 hours at room temperature.
It was exposed outdoors in water vapor at 0°C and left in a desiccator for a predetermined period of time.

After a predetermined period of time, keep the sample temperature at 20°C for 4 hours or more and measure the hardness according to JIS-6801 (paragraph 5, 2).
Measured using a JISA type hardness meter.

■How to evaluate and display test results environmental protection 1-1 Water resistance: tTIS-5400 (7.

2) Judgment ``soaked in water'' If there is no abnormality, 1' is 1) ○, others were marked ×.

1- & salt water resistance? JIS-ni-5400 (7.

0 NaCl as determined by Section 6) There is no abnormality even if it is immersed in a lithium solution. If there is no °1, ○, 2... Others were marked as ×.

1-&Weather resistance: When compared with the sample product, the case where there is no wrinkle, blistering, peeling, cracking, discoloration, or yoking is rated as 01, and the other is x.

&Adhesiveness 2-1 Base adhesion: JIS-5400 (6.

Judgment from the 15th foundation exam) Evaluation score of 8 or higher is ○, 6 or higher The bottom is marked with an x.

g-1 Recoating adhesion: JIS-5400 (6#1
01 evaluation score if it is determined that there is no problem in overcoating according to the 0 item (overcoating suitability), and the evaluation score is 8 or higher according to JIS-5400 (6, 15 item basic standard test). 6 or less was marked as ×. Also, there is no problem in applying 0 layers!・Those that were not determined to be ``9'' were marked with a ×.

& flexibility 8-1 Impact resistance: JIS-5400 (6.

18.3) Due to deformation due to the blow, It was determined that it was not possible to Mark the items as ○, and mark the other as ×. did.

4, @Toughness 4-1 Pencil hardness: JIS-5400 (item 6114)
A pencil scratch value of 2 or more was rated as ○, H and F was △, and HB or less was rated as ×.

6. Chemical resistance 5-1 Acid resistance: JIS-5400 (7.

8゛s-i alkali resistance: JIS-54001 (7,4
Items that were judged to have no abnormality even when immersed in alkali were marked ○, and others were marked ×.

a Painting workability: The finished state after drying was rated ○ without any aesthetic abnormality such as sag or surface unevenness, and the others were rated poor.

i. Viscosity stability = (A) butyl rubber paint component and (B) cement component added in predetermined amounts of each anti-rust paint is stored at room temperature for 8 months, and the viscosity change of the storage diameter is ±. Items within 104 were marked as ○, and other items were marked as X.

(20) Table 2 Test Results Table 2 As is clear from the test results in Figure 1, Example 1.
11 is water resistance, salt water resistance, environmental barrier properties represented by weather resistance, adhesion properties represented by base adhesion and recoat adhesion, flexibility represented by impact resistance and bending resistance, and lead foil. It was excellent in toughness represented by hardness, chemical resistance represented by 5 alkali resistance, viscosity stability, and painting workability, and met the purpose of the present invention.

In addition, the test results shown in Figure 1 clearly show that the anticorrosive paint of the present invention further improves the surface hardness due to moisture. This shows that the characteristics of cement components are also utilized.

Comparative Example 1 is a case where the amount of component 03) is 50 parts by weight or less per 100 parts by weight of component (A) of the present invention, and the toughness is 1.
“Inferior to ”.

Comparative Example 4 is a case where the component (B) is 500 parts by weight per 11 parts by weight of the component (A) of the present invention, and has excellent environmental barrier properties, adhesiveness, flexibility, chemical resistance, painting workability, Poor viscosity stability. Pa.

From the above, it can be seen that the anticorrosive paint of the present invention has both the advantages of the butyl rubber component and the advantages of the cement component, and covers the drawbacks of each.

In other words, the environmental barrier properties and flexibility derived from the butyl rubber component,
Cement F has the advantage of adhesion and overcomes the disadvantages of insufficient hardness and adhesion of the paint film due to the butyl rubber component, and overcomes the disadvantages of cracking and the need for long-term curing due to the cement 1 component. Due to the strong bond between the butyl rubber component and the cement component, it was possible to achieve good chemical resistance even when a large amount of cement component was contained, and it was also possible to generate economic benefits.

In addition to the above-mentioned merits, the anti-rust paint of the present invention also has C.
k) Contains 50 to 500 parts by weight of cement component (per 1 part by weight of butyl rubber paint component), so it inevitably becomes a high solids content paint, which allows for thick coating and reduces the number of coats. There are many advantages in terms of process reduction, labor saving, energy saving, cost reduction, stabilization of corrosion resistance, improvements in occupational safety and health and environmental protection due to the reduction in the amount of volatile solvents, and low paint prices. (24) When using butyl rubber, which is obtained by recycling automobile tire tubes as a butyl rubber component, rather than the length, which has a great advantage, the advantage of effective use of resources is also taken into account.

In this way, the anticorrosive paint of the present invention is a paint in a new field that combines the advantages of butyl rubber components and cement components that have not been seen in the conventional paint field, and also has the benefits that come with both. By exhibiting environmental barrier properties, flexibility, etc., and greatly extending the life cycle of the coated object,
It is useful for various industrial development 1.1.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the relationship of moisture to the hardness of the anticorrosive paint according to the present invention after drying and curing. 1... Hardness in water vapor at 80°C (Shore A) 2...
Outdoor 111 dew 8...in desiccator. Procedural amendment March 21, 1980 Patent Application No. 18421 2, Name of the invention Rust-preventing paint 3, Relationship with the person making the amendment Patent applicant Hayakawa Rubber Co., Ltd. (1) Specification page 1 Special iFl in lines δ to ]9: The statement in claim 1 is corrected as follows. [2. Claims L (AJ) A rust-preventing paint characterized by comprising a butyl rubber paint component comprising a color vehicle, a filler, an additive, and an organic solvent, and 5 (Bl) a cement component. ) In the composition of the color vehicle constituting the component, the butyl rubber component is butyl rubber, butyl recycled rubber] species or 2
10. The anticorrosive paint according to claim 1, characterized in that it is formed by using a seed in combination. & The anticorrosive paint according to claim 1, wherein the butyl rubber component in the composition of the color vehicle constituting the component (A) is recycled butyl rubber. The anticorrosive paint according to claim 1, characterized in that it contains 50 to 500 parts by weight of a cement component as component (B) per 100 parts by weight of component (A). J thing

Claims (1)

[Scope of Claims] 1. A rust-preventing paint comprising: (4) a butyl rubber paint component consisting of a color vehicle, a filler, an additive, and an organic solvent, and -03) a cement component. In the composition of the color vehicle constituting component (4) above, the butyl rubber component is one or two types of butyl rubber and butyl recycled rubber.
11. The anticorrosive paint according to claim 1, characterized in that it is formed by using a seed in combination. & The rust-preventive paint according to claim 1, characterized in that the butyl rubber component in the composition of the color vehicle that removes the reed content is butyl recycled rubber.Table (A) For 100 parts by weight of the component, (B) [
i12. The anticorrosive paint according to claim 1, characterized in that it contains 50 to 500 parts by weight of Cement (Cement), which is 19 minutes.